Dyeing of polyvinyl halide-acetate copolymer fibers and fabrics



Patented Oct. 1Q, 1944 DYEING F EPOLYVIN'YL HALIDE-ACETATE COPOLYMER. FIBERSAND FABRICS Roy Herman Kienle and Frederick Edward Petkc,

Bound Brook, N. J., assignors to American Cyanamid Company, 1%

tion of Maine wYork, N. Y a corpora- No Drawing. Application December 16,1939, Serial No. 309,608

8 Claims.

This invention relates to the dyeing of fibers and fabrics made from polyvinyl halide-acetate copolymers. y

The new fibers and fabricsproduced from polyvinyl halide-acetate copolymers and which are known under the trade .name of Vinyonhave shown important properties.- However, the dye I of polyvinyl halide-acetate copolymer material.

with oil soluble colors in the absence of. a solvent for the material but in the presence or a dyeing assistant which may be either an amine, a phenol,- an ester, or .an open chain ether. These compounds as used herein do not dissolve the resin. They may cause a swelling of the resin and it is possible that this property may in some cases be a factorin the excellentlevel dyeings which are possible by the use of the assistants of ent invention.

In the present invention, the term solvent is used in its common meaning. Theoretically some swelling agents, if used in extremely large the presquantities, are capable of dissolving a small amount of polyvinylhalide-acetate copolymers to 'form homogeneous liquids which might be termed solutions. For the purposeof the present invention, however, the term "solvent isused in its ordinary restricted meaning of a material capable of dissolving considerable quantities of polyvinyl halide-acetate copolymer to form true solutions containing substantial percentages of the copolymer. It should be understood that this term is used throughout this specification and claims in this common sense only.

It is an advantage of the present invention that full shade, uniform dyeings are obtained without in any way damaging the fiber: or the fabric, without causing shrinkage and with no substantial loss in strength. In general the dye baths of the present invention are aqueous solutions, the oil soluble colors and assistants being dispersed or emulsified in th bath. The present invention is not limited to any particular type of bath and it is an advantage that the dyeing technique which has been employed in the dyeing of cellulose acetate material can .be followed except that temperatures should not exceed 70C.

and preferably should not exce d 65 C Higher temperatures maybe used .but then a change occurs in the fabric such as shrinking. i

The present invention depends on'theuse or I a non-solvent or swelling assistant, the quantity being kept suillciently low .so' that no ,objection- I able efiect'on the material results. Minute quantities ofsolventmay ofcourse be present without affecting the strength or desirable'characteristics of the dyed material, but theyshould not be present in sufiicient amounts to have. any substantial solvent effect. In the specification and claims of'the present case the term substantial absence of solvents is intended to cover all cases where 'there.is no solvent at all, or, if any, it occurs in such minute quantities as to have no sub stantial effect on thematerial.

The method ofi'orming a dye bath according to the present invention may vary within wide limits and is not critical, which is an advantage of the present invention. ,The dyes and assistants may be separately dispersed and emulsified and then added to a dye-bath either in powder or paste form or the dye bath may be made up with the color and assistant or assistants dispersed therein afterwards. The results are sub-.- stantially the'same no matter how the baths are made up provided the same formula is used and this lack of critical procedure is a practical operating advantage of the present invention, A single assistant may be usedin a particular dye, bath, or a plurality of assistants may-be em ployed. -Frequently a dispersing agent may be added to the dye bath. The present. invention, however, is not sensitive to the particular -dis.. persing agent employed so long as it is not a solvent for the material to be dyed, but :we have found that ammonium caseinate is useful and one'of the preferred dispersing agents.

The present invention is applicable to oil soluble colors and more generally to those colors which can be used in dyeing cellulose acetate materials especially when the proper assistant is Q employed.

The present invention ls-not l-ir'r'iited to any particular amount of assistant. However, the amount used should be suiilcient toaffect the surface of the material to be colored. Use of an assistant in amounts beyond this effective amount does not give improved results and may waste assistant. The particular amount to be used will depend somewhat with the assistant and with the dye bath. In general, it is of the order of bright blue.

The invention will be described in greater detail in conjunction with the following specific exe amples which illustrate typical dye baths; but;

liimted to the examthe invention is in no way ples set forth.

Ezamplelf iEsample 6..

5 parts of Vinyonf yarn is dyed as follows: .18 part of a dispersible powder which is prepared by pasting .10 part of a dispersed red dye (prepared by coupling diazotized p-nitroaniline with phenyl ethyl ethanolamine) with 0.05 part ..of triphenylphosphate, 0.10.pa rt of a 15% am- Emonium -1caseinate solution, ;0.01 part soap and parts of Vinyon" yarn is dyed as follows: 0 1 I 0.10 part of a dispersed oil-soluble color which is made by coupling diazotized p-nitroanilirie on? dimethyl aniline and reducing the nitro group, 0.10 part alpha naphthol, 0.05 part of benzophenone, and 0.30 part of a ammonium caseinate solution are pasted together and added to 150 partsof'water- ThQdyein'g is carried out for 1 hour at 150 F.. 'in this bath. The 'color'is nearly completely exhausted to give a level; noncrocking dyeing. i

j Erarnplez N 5 parts of "Vinyon'is dyed inthe following manner:

follows I 0.05 part of a 10% solution of dioctyl sodium sulfosuccinate and drying this paste in the vacuum oven below 50 C is pasted with 0.5 cc. of a 5% r soap solution and diluting with 150 parts of water. Theyarnisdyed in this bath for 1 hour at 150 The color is exhausted and the yarn is dyed a brightscarlet which does not crock or sublime.

; Ea:ample 7 5 partsof FlVinyon" knit goods are dyed as 0.10 part of dispersed l-ethylamino--ethanol- :amino,;anthraquinone and 0.05part of a dispersed yellow dye, made by coupling cresidine di- "azo withp-amino acetanilide'arid saponifying,

A dye'bath is prepared"containing 0.10 part of a dispersed color which is made by couplingdiazotized p-nitroa'niline on phenyl ethyl ethanolamine,0.05 part of diphenyl ether, 0.30 part ofa 10% ammonium c'aseinate solution, and 150 parts of water. The dyeing is carried out forl hour at 150 F; 'Thecolor is exhausted well and gives a level dyeing which does not crock or sublime.-

' Empires 1 5 parts'of Vinyon" yarn-is dyed as follows:

the prior art as described in the Rugeley patent 0.10 part or'a dispersed oil-soluble color prepared by cdupling dlazotized 'p-nitroaniline'on pxylidine, 0.10part of diamyl phthalate' and 0.30

' part of a 10% ammonium caseinatesolution are pasted together and then addedto 150 parts" of water. The yarn is dyed in this bath for 1 hour at 150 F. The color" is'exhausted very well to give a level dyeing which does not crock or sublime.

Example-i 5 parts of askein of vinyonl is ,dyedin-the following manner: 1A dye bath is prepared containing 0.05 part of of the copolymer.

xylene azo betanaphthol, 2 parts of aniline,.0.10

.part of dioctyl sodium sulfosuccinatewhich issued as the wetting agent, and 150'partsof water.

. The skein is dyed for-30 minutes at 130 F.. The

bath is exhausted-and the fiber is uninjured.

The dyeing obtained is level anddoes not crock Example 5 V 5 parts of Vinyon staple fiber is dyed as follows: a t

0.10 part of dispersed l-ethylamino-4-ethanol-' amino anthaquinone are pasted with 0.10 part nbutyl-phenyl acetate,=0.30 part of a 10% ammoniunrcaseinate solution, and 0.30 part of a 10% ammonium linoleate solution. This" paste is diluted with 100 parts of water at 100 F. The.

fiber is dyed in this bathfor l'hourv at 150 F. The bath is exhausted and the fiber is dyed a are pasted'with 0.05 part' 'o'fn-butyl-phenyl-acetate, 0.30 part of a 10% solution of ammonium casein'ate and-0.30 part of a 10% solution of ammonium linoleate. This paste is diluted with 150 part's'of water." The knit goods are dyed for 1 hour at 150- F. This procedure'gives a'bright gi-eeri' dyeing which does "not crock or sublime.

' 'The'present -inventionnot'only provides an improved process for dyeing, materials containing polyvinyl halide-acetate copolymers, but it also produces new colored products; "The dyed products ofthe preseht'invention differ from those of above referred' to; by thefact the surface of the material shows-nodetectable deterioration as compared with the corresponding undyed material, whereas in the prior art processes, unless extreme precautionary'measuresare taken, a sur- "face deterioration and loss of strength can be detected. The dyed material of the present invention contains at least one oil soluble color, a small amount-of the dyeing assistant used, and is free fromsolvents for the polyvinyl halide-acetate co- Whatweclaim is: .i-

1. A method of dyeing polyvinyl halide-acetate copolymer containing materials which comprises subjecting the material to the action of a dye bath containing an oil soluble color and from 1 to 3% ofa phthalate, ester based on the weight 2. A method'oi dyeing. polyvinyl halide acetate copolymer containing, materials which comprises subjecting the, material to theaction of a dye bath containing-an oil soluble color and from 1 to 3% of an alkylphenyl acetate based on the weight of the copolymer.- i

3. A method of dyeing. polyvinyl halide-acetate copolymer containing materialswhich comprises subjecting the material to the action of an'aqueoilsv bath containing a dispersed oil-soluble color and from -1.3% of at least one ester which is a non-solvent for the copolymer and liquid at temperatures below C., the dyeing taking place in the substantial absence of organic solvent for the material. a

4. A method of dyeing poyvinyl halide-acetate copolymer. containing materials which comprises subjecting thematerial to the action of an aqueous bath containing a dispersed oil-soluble color and'froni 1-3%:.-of at least-one ester which is a non-solvent for the copolymer, and liquid at temsubstantial absence of organic solvent for the.

material at that temperature.

6. A colored polyvinyl halide acetate copolymer containing material showing no detectable deterioration as compared with the corresponding uncolored material, the colored material containing an oil-soluble color and from 1 to 3% of an ester which is a non-solvent for the copolymer and a liquid below 70 C., the colored material being further substantially free from organic solvents for the copolymer.

7. A colored polyvinyl halide-acetate copolymerester containing material showing no detectable deterioration as compared with the corresponding uncolored material, the colored material containing an oil color and from 1 to 3% of a phthalate ester based on the weight of the copolymer.

8. A colored polyvinyl halide-acetate ester containing material showing no detectable deterioration as compared with the correspqnding uncolored material, the colored material containing an oil color and from 1 to 3% of an alkyl phenyl acetate based on the weight of the co polymer.

ROY HERMAN KIENLE. FREDERICK EDWARD PETKE. 

